Insight of DFT and ab initio atomistic thermodynamics on the surface stability and morphology of In2O3

Zhang, Minhua; Wang, Wenyi; Chen, Yifei

doi:10.1016/j.apsusc.2017.11.258

Cited by 51 publications

(20 citation statements)

References 74 publications

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“…It should be remarked that such a model is solid, since the typical particle size is significantly larger than 3.5-4 nm, below which deviations from the equilibrium geometry might be plausible. Recent theoretical and experimental studies [29][30][31] support the formation of nanooctahedra under oxygen-rich atmospheres, such as that applied upon calcination. Although the computations by Chen et al [30] suggest a truncated-cube as the thermodynamically more stable morphology of the oxide under CO 2 hydrogenation conditions, analysis of In 2 O 3 after reaction shows negligible restructuring [10].…”

Section: Catalyst Propertiesmentioning

confidence: 99%

Mechanism and microkinetics of methanol synthesis via CO2 hydrogenation on indium oxide

Frei

Capdevila‐Cortada

Garcı́a-Muelas

et al. 2018

Journal of Catalysis

245

252

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Indium oxide has emerged as a highly effective catalyst for methanol synthesis by direct CO 2 hydrogenation. Aiming at gathering a deeper fundamental understanding, mechanistic and (micro)kinetic aspects of this catalytic system were investigated. Steady-state evaluation at 5 MPa and variable temperature indicated a lower apparent activation energy for CO 2 hydrogenation than for the reverse watergas shift reaction (103 versus 117 kJ mol À1), which is in line with the high methanol selectivity observed. Upon changing the partial pressure of reactants and products, apparent reaction orders of À0.1, 0.5, À0.2, and À0.9 were determined for CO 2 , H 2 , methanol, and water, respectively, which highlight a strong inhibition by the latter. Co-feeding of H 2 O led to catalyst deactivation by sintering for partial pressures exceeding 0.125 MPa, while addition of the byproduct CO to the gas stream could be favorable at a total pressure below 4 MPa but was detrimental at higher pressures. Density Functional Theory simulations conducted on In 2 O 3 (1 1 1), which was experimentally and theoretically shown to be the most exposed surface termination, indicated that oxygen vacancies surrounded by three indium atoms enable the activation of CO 2 and split hydrogen heterolytically, stabilizing the polarized species formed. The most energetically favored path to methanol comprises three consecutive additions of hydrides and protons and features CH 2 OOH and CH 2 (OH) 2 as intermediates. Microkinetic modeling based on the DFT results provided values for temperature and concentration-dependent parameters, which are in good agreement with the empirically obtained data. These results are expected to drive further optimization of In 2 O 3-based materials and serve as a solid basis for reactor and process design, thus fostering advances towards a potential large-scale methanol synthesis from CO 2 .

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Section: Catalyst Propertiesmentioning

confidence: 99%

Mechanism and microkinetics of methanol synthesis via CO2 hydrogenation on indium oxide

Frei

Capdevila‐Cortada

Garcı́a-Muelas

et al. 2018

Journal of Catalysis

245

252

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“…Recently, In 2 O 3 had attracted more attention because of its specific catalytic properties. The oxygen vacancy played a vital part in CO 2 adsorption and activation for the In 2 O 3 catalyst , and exhibited a superior catalytic activity over 300 °C in the progress of CO 2 hydrogenation to CH 3 OH. , The In 2 O 3 catalyst had shown a promising potential in CO 2 hydrogenation to CH 3 OH. Under the same conditions, the In 2 O 3 catalyst performed a better CH 3 OH selectivity and stability compared with the Cu/Zn/ZrO 2 catalyst. , Additionally, the reaction rate over In 2 O 3 was only decreased moderately in the presence of H 2 O at 300 °C, while the activity of a conventional Cu/Zn/Al 2 O 3 catalyst was decreased rapidly due to the added H 2 O .…”

Section: Introductionmentioning

confidence: 98%

“…The oxygen vacancy played a vital part in CO 2 adsorption and activation for the In 2 O 3 catalyst 14,15 and exhibited a superior catalytic activity over 300 °C in the progress of CO 2 hydrogenation to CH 3 OH. 16,17 The In 2 O 3 catalyst had shown a promising potential in CO 2 hydrogenation to CH 3 OH. Under the same conditions, the In 2 O 3 catalyst performed a better CH 3 OH selectivity and stability compared with the Cu/Zn/ZrO 2 catalyst.…”

Section: Introductionmentioning

confidence: 99%

Cu₂In Nanoalloy Enhanced Performance of Cu/ZrO₂ Catalysts for the CO₂ Hydrogenation to Methanol

Gao

Song

et al. 2020

Ind. Eng. Chem. Res.

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In this work, compared with non-Cu2In nanoalloy counterpart Cu-In/ZrO2 catalysts, a Cu1In2Zr4-O catalyst with the structure of Cu2In alloy exhibited an excellent performance for CO2 hydrogenation to CH3OH. CO2 conversion (12.8%) and methanol selectivity (72.8%) were outstandingly higher, which indicated that the synergetic effect existed between Cu and In over the Cu1In2Zr4-O catalyst. The formation of Cu2In alloy caused high dispersion of the active species and high surface area of the Cu1In2Zr4-O catalyst, enhancing catalyst reduction performance. Strong adsorption of CO2 caused a good conversion property of the Cu1In2Zr4-O catalyst. The strong interaction between the In and Cu species formed a nanoalloy and decreased the catalyst reduction temperature, which led to the high catalytic performance for CO2 hydrogenation. The Cu2In alloy rather than metallic Cu was the key active site for the methanol formation.

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“…Since then, the In 2 O 3 based catalyst attracts increasing attentions for CO 2 conversion with more and more publications in top journals. These published works include the further studies on the preparation and characterization of In 2 O 3 for CO 2 activation and hydrogenation [12][13][14][15] , the combination of In 2 O 3 with other oxides (like Ga 2 O 3 [16] and ZrO 2 [17][18][19][20] ) to improve the catalytic performance and the addition of metals to In 2 O 3 for the enhanced hydrogenation activity. Palladium [21][22][23][24] , platinum [25] , copper [ 26 , 27 ] and cobalt [28] have been successfully applied.…”

Section: Introductionmentioning

confidence: 99%

Selective hydrogenation of CO2 to methanol over Ni/In2O3 catalyst

Jia

Sun

Wang

et al. 2020

Journal of Energy Chemistry

194

131

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Insight of DFT and ab initio atomistic thermodynamics on the surface stability and morphology of In2O3

Cited by 51 publications

References 74 publications

Mechanism and microkinetics of methanol synthesis via CO2 hydrogenation on indium oxide

Mechanism and microkinetics of methanol synthesis via CO2 hydrogenation on indium oxide

Cu₂In Nanoalloy Enhanced Performance of Cu/ZrO₂ Catalysts for the CO₂ Hydrogenation to Methanol

Selective hydrogenation of CO2 to methanol over Ni/In2O3 catalyst

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Insight of DFT and ab initio atomistic thermodynamics on the surface stability and morphology of In2O3

Cited by 51 publications

References 74 publications

Mechanism and microkinetics of methanol synthesis via CO2 hydrogenation on indium oxide

Mechanism and microkinetics of methanol synthesis via CO2 hydrogenation on indium oxide

Cu2In Nanoalloy Enhanced Performance of Cu/ZrO2 Catalysts for the CO2 Hydrogenation to Methanol

Selective hydrogenation of CO2 to methanol over Ni/In2O3 catalyst

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Cu₂In Nanoalloy Enhanced Performance of Cu/ZrO₂ Catalysts for the CO₂ Hydrogenation to Methanol